See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/372746757

A comprehensive insight into the thermal runaway issues in the view of

lithium-ion battery intrinsic safety performance and venting gas explosion
hazards

Article in Applied Energy · July 2023

DOI: 10.1016/j.apenergy.2023.121651

CITATIONS READS

11 100

9 authors, including:

Gang Wei Ranjun Huang

Tongji University Tongji University
8 PUBLICATIONS 25 CITATIONS 9 PUBLICATIONS 32 CITATIONS

SEE PROFILE SEE PROFILE

Bo Jiang Jiangong Zhu

Tongji University Tongji University
53 PUBLICATIONS 890 CITATIONS 94 PUBLICATIONS 2,081 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Gang Wei on 07 December 2023.

The user has requested enhancement of the downloaded file.

 Applied Energy 349 (2023) 121651

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

A comprehensive insight into the thermal runaway issues in the view of

lithium-ion battery intrinsic safety performance and venting gas
explosion hazards
Gang Wei a, b, Ranjun Huang a, b, Guangxu Zhang a, b, Bo Jiang a, c, Jiangong Zhu a, b,
Yangyang Guo e, Guangshuai Han d, e, *, Xuezhe Wei a, b, Haifeng Dai a, b, **
a
School of Automotive Studies, Tongji University, Shanghai 201804, China
b
Clean Energy Automotive Engineering Center, Tongji University, Shanghai 201804, China
c
Postdoctoral Station of Mechanical Engineering, Tongji University, Shanghai 201804, China
d
Institute for Advanced Study, Tongji University, Shanghai 200092, China
e
Shanghai AI NEV Innovative Platform Co., Ltd., Shanghai 201804, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• The intrinsic safety of batteries is

compared based on TR evolution An illustration of a framework for comprehensive understanding of thermal runaway issues involving
features. lithium-ion batteries.
• LFP batteries exhibit greater TR toler­
ance and lower TR hazards than NCM
batteries.
• Venting gas components and explosion
characteristics are quantitatively
analyzed.
• Venting gases for LFP batteries show a
higher explosion risk than NCM
batteries.
• Micro-overcharged NCM batteries
demonstrate lower TR tolerance and TR
hazards.

A R T I C L E I N F O A B S T R A C T

A comprehensive understanding of thermal runaway (TR) features and battery venting gas (BVG) explosion
characteristics is the critical issue of thermal hazard prevention. In this study, commercial-size lithium-ion
Keywords: batteries with LiFePO4 (LFP) and Li(NixCoyMnz)O2 (NCM, x from 0.5 to 0.8) cathode materials, as well as the
Commercial-size lithium-ion batteries
micro-overcharged cells, are triggered to TR under adiabatic conditions using an accelerating rate calorimeter. In
Thermal runaway
Intrinsic safety performance
addition, the obtained BVG is transferred into the gas chromatograph for further component identification.
Venting gas explosion hazards Subsequently, the specific values of the intrinsic battery safety performance (TR tolerance and TR hazards) and

* Correspondence to: G. Han, Institute for Advanced Study, Tongji University, Shanghai 200092, China
** Correspondence to: H. Dai, School of Automotive Studies, Tongji University, Shanghai 201804, China
E-mail addresses: sdlyshuai0104@163.com (G. Han), tongjidai@tongji.edu.cn (H. Dai).

https://doi.org/10.1016/j.apenergy.2023.121651
Received 9 May 2023; Received in revised form 14 July 2023; Accepted 23 July 2023
Available online 29 July 2023
0306-2619/© 2023 Elsevier Ltd. All rights reserved.
G. Wei et al. Applied Energy 349 (2023) 121651

Cathode material BVG explosion risks (lower explosion limits, LEL) are calculated. The results show that, from the perspective of
Micro-overcharge battery TR evolution features, LFP batteries have greater TR tolerance than NCM batteries. Moreover, the TR
hazards of NCM batteries are more severe than LFP batteries and worsen with increasing nickel content, which is
proved by ambient temperature and post-disaster analysis. The primary types of BVG consist of hydrogen, carbon
monoxide, carbon dioxide and hydrocarbon gases for both LFP and NCM batteries. However, due to the sig­
nificant amount of hydrogen and hydrocarbon gases with low LEL values, the LEL values of BVG for LFP batteries
are lower than NCM batteries, demonstrating the higher deflagration risks for the former. Besides, the LEL values
of NCM batteries' BVG increase with higher energy density. A single micro-overcharge leads to lower TR
tolerance and TR hazards but has little effect on LEL values for NCM cells. It is obvious that the safety issues
associated with LFP batteries should also be given sufficient attention to avoid system-level explosions. The
quantitative evaluation results of this paper provide new ideas for battery intrinsic safety performance assess­
ment and a clear direction for mitigation strategy of battery TR-related secondary disasters.

1. Introduction
Clean energy has gained significant attention due to the evolving
global energy structure and the peaking carbon dioxide emissions and
carbon-neutral policies of China [1]. Lithium-ion batteries (LIBs) stand
out among various electrochemical power sources due to their high
energy density and prolonged cycle life [2,3]. They are widely employed
in transportation, consumer electronics, and large-scale energy storage
systems (ESS) [4,5]. The energy density of lithium-ion batteries has been
continuously increasing in recent years to alleviate consumers' concerns
regarding the range of electric vehicles (EVs) [6]. However, the resulting
battery safety issues and electric vehicle safety accidents hinder the
further large-scale popularization of EVs [7–9].
Electric vehicle safety accidents are usually caused by battery ther­
mal runaway (TR). Battery TR, an irreversible disaster-causing failure
mode, occurs when a battery experiences a specific type of abuse
[10,11]. Mechanical abuse (chassis deformation and foreign body
infiltration) [12,13], electrical abuse (overcharge and over-discharge)
[14,15], and thermal abuse (battery thermal management system
(BTMS) failure leading to abnormal battery heating) [2] are the three
main types of abuse. The macroscopic features of the battery TR include
an exponential temperature rise in a short period, a steep drop in
voltage, the release of large amounts of flammable and toxic gases, jet
fire, and even explosion [9]. All of these would cause severe damage to
the personal and property safety of passengers [10].
Many researchers have investigated the behaviors of battery com­
ponents by decoupling them due to the complexity of side reactions
causing battery TR. In terms of electrolytes, Botte et al. [16] used dif­
ferential scanning calorimetry (DSC) to evaluate the heat-release prop­
erties of commercial electrolytes. They discovered that the lithium salt
concentrations and solvent ratios substantially impact those properties.
As for the anode material, Zheng et al. [17] evaluated the heat and gas
generation mechanism of lithiated graphite (LixC6) with each electrolyte
component using DSC and Synchronous thermal analyzer-mass spec­
trometry (STA-MS) and found a three-stage exothermic reaction:
decomposition of the solid electrolyte interphase (SEI) film; the reaction
of (LixC6) with ethylene carbonate (EC) and lithium hexa­
fluorophosphate (LiPF6); the reaction of LixC6 with the binder. Bak et al.
[18] used in situ time-resolved X-ray diffraction-mass spectrometry (TR-
XRD/MS) to systematically assess the heat generation and oxygen-
release behavior of nickel-rich lithium-ion batteries (Li(NixCoyMnz)O2,
NCM, x + y + z = 1) with various nickel ratios. They revealed that the
thermal decomposition temperature gradually decreases, and the
released amount of oxygen increases as the nickel content increases,
degrading the safety of high‑nickel batteries [18]. Moreover, Moutchou
et al. [19] also compared the thermal behaviors of the Li(Ni0.8C­
o0.1Mn0.1)O2 (NCM811) layered cathode and lithium iron phosphate
(LFP) olivine cathode under the full state of charge (SoC). They found
that the latter has higher thermal stability. They noted that this is due to
the stable P–O covalent bond in the LFP cathode. In contrast, the
transition metal‑oxygen bond of the NCM811 cathode is polar and easily
releases active oxygen [19].
The battery cell is the smallest physical unit of the battery pack
applied in the EVs and ESS. Thus, it is also essential to study the electro-
thermal coupling characteristics of a single battery cell during TR.
Regardless of the abuse form, the occurrence of battery TR is eventually
ascribed to a significant amount of excessive heat production that
cannot be sufficiently dispersed [11]. As a result, numerous in­
vestigations on battery TR characteristics have been carried out using
auxiliary heat sources. Additionally, as far as we know, the types of heat
sources offered are varied, including heating plates [20], vent sizing
package 2 (VSP2) [21], cone calorimeter [22], extended-volume accel­
erating rate calorimeter (EV-ARC) [23], homemade confined combus­
tion chamber [24], electromagnetic inductive heating coils [25], high
power short-time laser irradiation [26], and fractional order thermal
runaway calorimetry [27]. Among them, EV-ARC is widely used for TR-
induced tests of large-capacity lithium-ion batteries due to its unique
step-by-step heating-adiabatic mode. Since Feng et al. carried out the
work, the characteristic temperature parameters of lithium-ion batteries
during the TR process, i.e., self-heating temperature T1, TR triggering
temperature T2 and maximum temperature T3, have been summarized
through extensive tests [28]. The temperature sequence is widely used
to evaluate the safety performance of a particular type of lithium-ion
battery.
As lithium-ion battery manufacturing technology develops, the
application variety of capacity and cathode material is increasing
significantly. First, to reduce the complexity of battery formation, the
capacity tends to be larger [29]; secondly, due to the difficult compat­
ibility of energy density and safety characteristics, various cathode
material-based batteries are adopted in different application scenarios,
e.g., LFP and NCM batteries [30]. Specifically, in pursuing long cycle life
and low cost, such as ESS with ultra-large installed capacity and auto­
motive power-oriented pioneering LIBs manufacturers, LFP batteries
have a more significant advantage [31]; the NCM batteries with high
energy density are widely used in EVs with extremely high range re­
quirements. Besides, NCM batteries are divided into three types, i.e.,
low-nickel-content (e.g., Li(Ni1/3Co1/3Mn1/3)O2 (NCM333)), medium-
nickel-content (e.g., Li(Ni0.5Co0.2Mn0.3)O2 (NCM523)) and high-
nickel-content (e.g., Li(Ni0.6Co0.2Mn0.2)O2 (NCM622) and NCM811)
[18]. Medium-nickel content battery is an optimized solution after
balancing thermal stability and energy density. However, product ter­
minals equipped with the above-all battery types have been subject to
safety accidents and even explosions [20,32], causing great public
concern and hindering the acceptance of LIBs. In addition to the rela­
tively large number of EV safety incidents, MWh-class ESS has not been
spared. In particular, the ESS explosion that occurred in April 2021 in
Dahongmen, Beijing, China, caused several casualties [33]. The battery
installed in this 25 MWh ESS is the LFP battery, which is generally
known to be safe from previous studies [19,30]. However, it is seen that
the hazard level of this accidental catastrophe is equally enormous and
unbearable compared with NCM battery-related disasters. Therefore,
conducting a safety performance assessment study on lithium-ion bat­
teries widely deployed in the current multi-application scenarios is ur­
gent and essential.

2
G. Wei et al.
A fire or explosion issue may occur in EV and ESS when the
combustible mixture venting from the battery reaches a certain amount
and contacts with sufficient air [34]. The solid phase component of the
mixture provides a local high-temperature hot spot, while the gas phase
component acts as a reducing agent [35]. Thus, battery venting gas
(BVG)-release behavior-related research is of great importance. Jia et al.
[29] and Zhou et al. [20] experimentally measured the venting gas ve­
locity, an important parameter characterizing battery TR behavior, and
they found the multi-peak feature corresponding to the electrolyte
vaporization and redox chemical reactions of TR, respectively. For
venting gas temperature, Zhou et al. [20] and Qin et al. [30] determined
values higher than 200 ◦ C, which provides certain trigger conditions for
gas deflagration. Moreover, Qin et al. [30] conducted thermal runaway
tests on a prismatic LFP battery pack and found that H2, NH3, CH4, C2H4,
CO and CO2 are the main composition of detected gases through
hydrogen probes and Fourier transformation infrared spectrometer
(FTIR). Among them, H2 accounts for around 38.86% of the BVG; be­
sides, the fact that fire and explosion are sparked by a high concentra­
tion of H2 and C2H4 is confirmed by numerical diffusion models. Peng
et al. [36] additionally found toxic gases such as HF, SO2 and NOx. Based
on this, two state-of-the-art fire-induced indices were developed to
assess the toxicity for people's safety, i.e., Fractional effective doze
(XFED) and Fractional effective concentration (XFEC) [10,29]. Apart from
the toxicity of the BVG, the explosion risk (Lower explosion limits, LELs)
is an equally important parameter related to the battery TR behaviors.
Yuan et al. [37] analyzed gas samples after different cathode material (i.
e., LFP, lithium titanate (LTO) and NCM) -based cylindrical battery
(maximum capacity is 3.8 Ah) TR using gas chromatograph (GC) and
found a large amount of flammable gases (e.g., H2, CH4, C2H2, C2H4 and
C2H6 etc.). Moreover, he noted that rapid dilution of H2 and CH4 with
low LELs in confined spaces is an important measure to prevent fires or
explosions; however, no further quantitative assessment was carried out.
Chen et al. [38] analyzed the effect of the external conditions (e.g.,
environmental temperature and heating power) on the LELs induced by
cylindrical NCM battery (capacity of 2.6 Ah). As mentioned above, in
practical applications, different cathode material-based battery is
deployed, and the capacity tends to be large. However, the study on the
quantitative explosion risk assessment of venting gas from the described
battery type is still lacking.
Based on the above analysis, four types of cathode material (LFP,
NCM523, NCM622 and NCM811 + NCM523)-based batteries with a
wide range of capacities are utilized. The adiabatic TR tests are con­
ducted in the accelerating rate calorimeter (ARC). Information such as
temperature and voltage during the thermal runaway process is
collected. The morphology of the failed batteries following thermal
runaway is recorded using the optical camera and observed by scanning
electron microscope-energy dispersive spectroscopy (SEM-EDS).
Furthermore, the BVG is collected and injected into the GC. Compared
with the previous studies, this work assesses the hazard degree of battery
safety accidents from a comprehensive perspective. On the one hand,
characteristic parameters, which have multiple properties during a
thermal failure evolution process, are used to characterize the intrinsic
safety performance of a battery. On the other hand, based on the GC test
results, the subsequent potential explosion risks of the BVG after large-
format battery TR are quantified.
The remainder of this study is structured as follows: Section 2 details
the lithium-ion batteries information and experiment bench, followed
by the collected data and analysis results in Section 3. Section 3.1 firstly
statistics TR-related characteristic parameters by analyzing the
electrical-thermal response curve. And then, the battery safety perfor­
mance is quantitatively assessed based on the key characteristic pa­
rameters. The critical failure features are given in Section 3.2. Section
3.3 presents the components, proportion, and explosion hazards
assessment results of the BVG. Finally, Section 4 summarizes the main
conclusions.
3
Applied Energy 349 (2023) 121651
2. Experiments
2.1. Lithium-ion batteries specifications
The commercial-size batteries with capacities ranging from 22 Ah to
195 Ah and energy densities ranging from 110 Wh⋅kg− 1 to 275 Wh⋅kg− 1
are utilized to more thoroughly evaluate the safety performance of
lithium-ion batteries at the stage of market application, as shown in
Fig. 1. Detailed information, i.e., battery number, package type and
mass, are listed in Table 1. The cathode materials include LFP, NCM523,
NCM622 and NCM811 + NCM523. It is clear that NCM lithium-ion
batteries account for the majority of the total and have a greater en­
ergy density, ranging from 230 Wh⋅kg− 1 to 275 Wh⋅kg− 1, which reflects
their popularity in the current market. LFP batteries are also involved,
which are more prevalent in the field of energy storage systems due to
their inherent safety. The anode materials are porous graphite. More­
over, batteries are packaged in prismatic and pouch types, respectively.
Clearly, the diversity of batteries provides a valid data source for
assessing safety performance.
2.2. Adiabatic TR tests
2.2.1. Preparation before adiabatic TR tests
Before adiabatic TR tests, all battery samples are charged to 100%
SoC, using a constant current-constant voltage (CC-CV) charging pro­
tocol (constant voltage charge at the upper cut-off voltage until current
lower than 0.05C) to explore the TR characteristics of the batteries in the
riskiest state. The upper charge cut-off voltage is specified by the man­
ufacturers, as shown in Table S1 (see supplementary data). The voltage
value employed for #G cells is an increase of 50 mV over the upper
charge cut-off voltage, aiming to explore the impact of a single slight
overcharge on the battery safety performance and following BVG
characteristics. The above process is performed on the NEWARE battery
test system (CT-4008-5V200A-NTFA, Shenzhen, China). The open-
circuit voltage at the initial moment at the beginning of the experi­
ment is shown in Table S1, ensuring the battery is in a specific SoC.
The N-type thermocouple inside the ARC cavity is utilized to deter­
mine the moment of battery self-heating and triggering TR. Further­
more, multiple K-type thermocouples (Fig. 2(a) and Fig. 2(g), GG-K-30-
SLE) are attached to the battery surface to obtain the maximum tem­
perature during the TR process. For the accuracy of temperature data
acquisition, both types of thermocouples are fixed and protected by glass
fiber tape (Fig. 2(g)). Moreover, the new K-type thermocouples are
utilized after each abuse test. Due to the variety of the package forms
Fig. 1. Capacity, energy density and number information of the tested cells.
G. Wei et al. Applied Energy 349 (2023) 121651

Table 1 interface, mainly including time-related parameters and temperature-

Detailed information of the tested batteries. related parameters.
Cell Cathode material Package Mass/ Capacity/ No. of The ARC is conducted in the following mode: heat-wait-search (H-W-
number g Ah GC S) mode. First, the batteries are heated up to the initial temperature.
tests Once the initial temperature is reached, the first calibration procedure is
#a1 LiFePO4 Prismatic 632.9 22 3 performed. The calibration process's time is changed to the other cali­
#a2 LiFePO4 Prismatic 639.2 22 3 bration time for all the following work-step cycles. The ARC then enters
#b LiFePO4 Prismatic 2997.7 162 3 the heating mode, increasing the cell surface temperature and chamber
#c1 LiFePO4 Prismatic 3262.2 195 3
#c2 LiFePO4 Prismatic 3281.1 195 3
temperature by 5 ◦ C through PID control algorithm. After that, it goes to
#A1 Li(Ni0.5Co0.2Mn0.3)O2 Prismatic 902.7 58 3 the waiting stage to create a consistent temperature distribution inside
#A2 Li(Ni0.5Co0.2Mn0.3)O2 Prismatic 902.3 58 3 the heated battery. The searching stage is used to search for abnormal
#A3 Li(Ni0.5Co0.2Mn0.3)O2 Prismatic 903.2 58 3 heat generation behavior inside the battery, i.e., whether the self-
#B1 Li(Ni0.6Co0.2Mn0.2)O2 Pouch 757.5 51 2
heating rate exceeds the set temperature rise threshold. If the self-
#B2 Li(Ni0.6Co0.2Mn0.2)O2 Pouch 763.9 51 3
#C Li(Ni0.6Co0.2Mn0.2)O2 Pouch 832.1 60 3 heating rate of the tested cells exceeds the temperature rise threshold
#D1 Li(Ni0.6Co0.2Mn0.2)O2 Prismatic 1425.9 90 3 without decay, the ARC automatically switches to adiabatic mode, and
#D2 Li(Ni0.6Co0.2Mn0.2)O2 Prismatic 1426.6 90 3 the temperature of the chamber is kept consistent with the temperature
#D3 Li(Ni0.6Co0.2Mn0.2)O2 Prismatic 1421.5 90 3 of the battery samples, in which all the abnormal heat generation is
#D4 Li(Ni0.6Co0.2Mn0.2)O2 Prismatic 1432.8 90 3
#E Li(Ni0.6Co0.2Mn0.2)O2 Prismatic 1802.1 115 2
utilized for self-heating. Otherwise, the ARC will go to the next H-W-S
Li(Ni0.8Co0.1Mn0.1)O2 cycle until the mentioned behavior occurs. Finally, ARC enters the
#F1 + Li(Ni0.5Co0.2Mn0.3) Pouch 1058.9 78.5 3 cooling mode when the cell surface temperature reaches the pre­
O2 determined cooling temperature.
Li(Ni0.8Co0.1Mn0.1)O2
#F2 + Li(Ni0.5Co0.2Mn0.3) Pouch 1060.7 78.5 3
O2 2.3. Characterization tests
Li(Ni0.8Co0.1Mn0.1)O2
#F3 + Li(Ni0.5Co0.2Mn0.3) Pouch 1061.7 78.5 3 An aluminum-plastic gas sampling bag, as shown in Fig. 2(e), is
O2 attached to the pressure relief valve of the ARC to collect the venting gas
Li(Ni0.8Co0.1Mn0.1)O2
#G1 + Li(Ni0.5Co0.2Mn0.3) Pouch 1060.8 78.5 3
after battery TR. The sampling bag is emptied beforehand to minimize
O2 the interference of impurity gases with the results. Additionally, for the
Li(Ni0.8Co0.1Mn0.1)O2 accuracy of the test results, the number of gas collections after each
#G2 + Li(Ni0.5Co0.2Mn0.3) Pouch 1059.5 78.5 3 adiabatic TR test is two to three times, as shown in Table 1, and the final
O2
results are averaged. The limited size of the ARC (cylindrical diameter of
Li(Ni0.8Co0.1Mn0.1)O2
#G3 + Li(Ni0.5Co0.2Mn0.3) Pouch 1059.6 78.5 3 500 mm × height of 500 mm) and the rapid collection of venting gases
O2 within minutes of the battery thermal runaway both maximize its
original composition. After that, an electric motor pumps the venting gas
from the sampling bag into the GC (Agilent 7890B) for analysis, as
shown in Fig. 2(d). Thermal conductivity detector (TCD) and hydrogen
and geometries, four types of arrangements are used. As shown in Fig. 2f
flame ionization detector (FID) are used in GC to detect, respectively,
(i), five K-type thermocouples marked Tfront1, Tfront2, Tside1, Tside2, and
inorganic small molecule gases (such as H2 and CO) and organic short
Tbottom are fitted to the geometric centers of the large surfaces, side
carbon chain hydrocarbon gases (such as CH4 and C2H4). The amount of
surfaces, and bottom surface of prismatic cells numbered a, b, A, D, and
each detected gas is presented as a mole proportion and is further uti­
E. Three K-type thermocouples, labeled Tfront1, Tfront2, and Tbottom, are
lized in the theoretical calculation of LELs. Argon serves as the carrier
attached to the geometric centers of the large surfaces and bottom face
gas.
of #c prismatic cells, as seen in Fig. 2f(ii). Three K-type thermocouples
After the adiabatic TR and GC tests, the ARC chamber is cooled to
marked Tfront1, Tfront2, and Tfront3 are fitted to various locations along the
room temperature. The chamber is then opened, and the battery re­
large surface's axis for #B and #C pouch cells, as shown in Fig. 2f(iii).
siduals are taken out and weighed to determine the mass loss ratio (the
For #F and #G pouch cells, three K-type thermocouples, labeled Tfront1,
ratio of mass loss to initial mass). The macroscopic characteristics of the
Tfront2, and Tside, are attached at different locations on large surface and
failed batteries are recorded by a camera. Especially for cells with
the geometric center of side surface, as depicted in Fig. 2f(iv). All TR
serious powdered electrodes, the corresponding mixed powder is
tests are equipped with an additional K-type thermocouple marked
collected and transferred to the SEM (JEOL JSM-7610FPLUS) to observe
Tambient to acquire the ambient temperature in the ARC cavity. The
the microscopic morphology, while the elemental composition is tested
battery voltage during the TR process is obtained by connecting the
by EDS (Genesis Apollo X).
voltage sampling line (Fig. 2(g)) to the battery tabs. As shown in Fig. 2
(b), the data logger (LR8450, HIOKI) records information about the
3. Results and discussion
multi-point temperature and voltage.

3.1. Electro-thermal characteristics analysis and safety performance

2.2.2. Experimental procedures to initiate adiabatic TR tests
evaluation
The adiabatic TR tests are carried out in the ARC (HEL BTC-500), as
shown in Fig. 2(c). The tested batteries are wrapped with electric
3.1.1. Features and mechanisms of temperature/voltage evolution
heating wire (Fig. 2(g)) to achieve homogeneous heating and suspended
As shown in Fig. 3, the temperature/voltage curves of NCM811 +
from the chamber cover of the ARC (Fig. 2(a)). Finally, the adiabatic
NCM523 (Figs. 3(a) and (b)), NCM622 (Figs. 3(c) and (d)), NCM523
chamber is sealed with bolts. Proper calibration and parameter settings
(Figs. 3(e) and (f)) and LFP (Figs. 3(g) and (h)) cells during adiabatic TR
are essential for large-format lithium-ion batteries to obtain reliable test
tests are displayed in detail. The temperature rise rate is obtained by
data. Likewise, parameter settings are also different due to the diversity
differentiating the temperature. Test results of other batteries are shown
of the batteries, as shown in Table S2 (see supplementary data) and
in Fig. S1 (see supplementary data), and there are some differences in
Table S3 (see supplementary data). The relevant parameters for per­
the response curves of each test.
forming adiabatic TR tests are set using the host computer operator
Considering the similarity of TR processes, the temperature rise rate

4
G. Wei et al. Applied Energy 349 (2023) 121651

Fig. 2. Experimental configuration: (a) Battery samples. (b) Data logger (LR8450, HIOKI). (c) ARC, HEL BTC-500. (d) GC, Agilent 7890B. (e) Aluminum-plastic gas
sampling bag. (f) Schematic diagram of K-type thermocouples layout: i-#a, #b, #A, #D and #E cells; ii-#c cells; iii-#B and #C cells; iv-#F and #G cells. (g)
Photographs of battery samples wrapped with the electric heating wire, K-type thermocouples and N-type thermocouple: i-#F1 cell; ii-#D1 cell; iii-#A2 cell; iv-
#c2 cell.

curve is divided into four stages according to the temperature sequence
defined by Ref. [28] and the moment when the massive internal short
circuit occurs. Specifically, T1 is the beginning of abnormal heat gen­
eration inside the battery; T2 implies a significant superimposed
exothermic reaction between the electrode materials; T3 contains the
information on the maximum energy that can be released by failed
battery's active material. A large-scale internal short circuit, i.e., a
sudden voltage drop, occurs [39]. The temperature at this moment can
be recorded as TM-ISC. As seen in Fig. 3, there are two types of recon­
structed temperature sequences, one is T1-TM-ISC-T2-T3 (Figs. 3(b), 3(d)
and 3(h)) and the other one is T1-T2-TM-ISC-T3 (Fig. 3(f)). The two tem­
perature values (TM-ISC and T2) are found to be quite close basically, as
listed in Table S4 (see supplementary data). The result is similar to
Ref. [40]. Combined with Fig. S1, the former temperature sequence is
the predominant type. Thus, the following analysis focuses on the
sequence T1-TM-ISC-T2-T3. Moreover, the characteristics of the voltage
response curve corresponding to each stage are explained.
Stage I: This stage starts with the H-W-S mode and ends at T1. The
temperature shows a step increase while causing a slow drop in voltage.
Meanwhile, the temperature rise rate points are densely distributed and
maintained in the low-value range.
Stage II: When the ARC detects that the temperature rise rate ex­
ceeds the set temperature rise threshold, the temperature at this point is
marked as T1. Typically, at this moment, the metastable components of
the SEI film begin to decompose [14]. The lithiated graphite, which is no
longer covered by the SEI film, reacts when it comes into contact with
the electrolyte [39]. Compared to the previous stage, the temperature
rise rate accelerates due to the above side reactions, as seen in Fig. 3(b),
(d) and (h). At the same time, the electrolyte evaporation causes an
increase in internal pressure. The main vaporized electrolyte compo­
nents in this stage are mainly DMC (boiling point of 91 ◦ C), EMC (boiling
point of 110 ◦ C) and DEC (boiling point of 125.8 ◦ C) [41,42]. When the
internal pressure of prismatic batteries reaches the specified values, the
safety valve opens and the temperature at this point is recorded as Topen.

5
G. Wei et al. Applied Energy 349 (2023) 121651

Fig. 3. Temperature/voltage curves and temperature rise rate curves of different cells. (a, b) #F1. (c, d) #D1. (e, f) #A2. (g, h) #c2.

6
G. Wei et al.
Through the statistics, it is discovered that the range of Topen is around
125–165 ◦ C. Following the pressure relief process, the temperature
showed a significant drop as a result of the gaseous substances ejection
effect, as shown in Fig. 3(c), Fig. 3(e) and Fig. 3(g). Nevertheless, the
temperature continues to rise after that due to the continuous internal
exothermic reaction. Pouch cells have low internal pressure tolerance
and thus do not exhibit significant temperature drop characteristics after
rupture, as shown in Fig. 3(a). There is also an interesting phenomenon
that the ARC repeatedly executes the heating step, as shown in Fig. S1(i),
Fig. S1(m) and Fig. S1(q), demonstrating that the exothermic reactions
inside the cell are not further deteriorated. The phenomenon indicates
that, in practical grouping scenarios, the further aggravation could be
avoided in this abnormal temperature range if the BTMS effectively
dissipates heat from the “question battery.”
Regarding the voltage response, it keeps gradually dropping during
the initial part of this stage. In Figs. 3(c) and (g), the voltage dropped
quickly due to the opening of the safety valve. The above phenomenon is
particularly obvious in Fig. S1(c) and Fig. S1(d). When the safety valve
breaks and the gas releases, the electrodes are out of alignment, which
might cause an internal short circuit (ISC) [43]. The voltage increases
Fig. 4. Statistics of characteristic parameters based on adiabatic TR tests. (a) T1. (b) T2. (c) Tmax. (d) Rmax.
7
Applied Energy 349 (2023) 121651
again once the safety valve finishes venting. However, overall, the
voltage has decreased significantly from its initial level. The shrinkage of
the separator when heated might be another cause of the ISC [44]. The
cut-off temperature for this stage is TM-ISC.
Stage III: The exothermic reactions still accelerate in this stage. The
separator also undergoes a large-scale meltdown and collapse, which
leads to the deterioration of the physical isolation effect between the
cathode and anode electrodes [45,46]. After that, a large-scale ISC
forms, releasing significant electrical energy and causing the tempera­
ture to rise at a rate of 1 ◦ C⋅s− 1 [9], i.e., the appearance of T2. Due to the
short duration of this stage, there is only a slight temperature difference
between the initial and end points, as shown in Figs. 3(b), 3(d) and 3(h).
Additionally, the open circuit voltage drops to zero basically at the end
of this stage. The presence of the other temperature sequence, i.e., T1-T2-
TM-ISC-T3, indicates that internal short circuits are not necessarily the
only critical factor in triggering TR. It is hypothesized that the
exothermic side reactions between active materials might be to blame
for this [45,47].
Stage IV: Once TR has fully begun, it cannot be stopped. Following
T2, the surface temperature increases exponentially to the maximum
G. Wei et al.
temperature T3. The points of the temperature rise rate curves in Fig. 3
gradually becomes discrete, clearly different from the initial dense dis­
tribution form of stage I. The difference between the onset and end
temperature is notable, as shown in Fig. 3, which is reflected by a rapid
increase in the temperature curves. The phenomena suggest that the
variety of side reactions is vibrant. Although the duration of this stage is
also short, the heat release is significant, and the damage to the battery is
enormous [15,45]. When the temperature reaches the set cooling tem­
perature, ARC automatically activates the cooling mode for mainte­
nance purposes, corresponding to the trailing part of the temperature
curves.
3.1.2. Statistics of feature parameters
A typical temperature sequence {T1, T2, T3} is used to extract the TR
properties of commercial-size lithium-ion batteries, which could help to
quickly dissect the TR behavior of a particular battery type and evaluate
the safety performance by comparing the values [28]. In this study, a
multi-position layout of thermocouples is employed to acquire the
maximum temperature due to its distribution inhomogeneity. The ob­
tained Tmax replaces T3 in the above temperature sequence, and the
specific values are shown in Fig. S2 (see supplementary data). To
effectively evaluate the safety performance of a battery more visually,
the above three characteristic temperature parameters, i.e., T1, T2 and
Tmax, are extracted from Fig. 3, Fig. S1 and Fig. S2. The specific data are
displayed in Fig. 4 and Table S4, which provides a quick overview of the
battery TR features. In addition, energy density is introduced as a
measure index of the performance of each characteristic parameter. The
colors in Fig. 4 represent the energy density of the battery, with the
darker colors corresponding to batteries with higher energy density and
vice versa.
Fig. 4(a) shows the statistics of T1, which is observed at about
54–140 ◦ C for all battery samples. The result is consistent with the range
of 60–120 ◦ C summarized by Ref. [9]. It is clear that the thermal stability
of commercial-size batteries with graphite-based negative electrodes has
improved recently because some values exceed 120 ◦ C. The correlation
between the T1 and energy density is weak since the temperature is
mainly associated with the degradation process of the anode SEI film
[8]. Moreover, a single micro-overcharge reduces the thermal stability
of the batteries, resulting in a significantly lower T1, as reported in
Ref. [39]. For instance, the T1 of #G2 cell is about 55 ◦ C lower than that
of #F1 cell. The reason is the occurrence of plated lithium which has a
high reactivity with the electrolyte. Additionally, it is found that having
a large capacity does not always mean poor thermal stability, as the 195
Ah LFP battery numbered #c2 has the greatest T1 value among all the
batteries.
The values of T2 are shown in Fig. 4(b), and the findings demonstrate
that the values are highly associated with the cathode material type and
energy density. According to statistics, the T2 for LFP cells is between
190 and 220 ◦ C, while the T2 for NCM cells is in the range of 140–175 ◦ C.
As suggested by Ref. [39], a single micro-overcharge has little effect on
the value of T2. It is worth noting that the value of T2 might be correlated
with the temperature at which the separator totally fails, because rele­
vant studies have shown that the melting points of PE and PP are 135 ◦ C
and 166 ◦ C, respectively [44,46]. For cells with T2 above 200 ◦ C, the
internal separator is perhaps an inorganic particle-polymer composite
film. Because even at >200 ◦ C, the composite film with ceramic coating
(e.g., Al2O3, SiO2 and TiO2, etc.) maintains its structural integrity [48],
which provides excellent physical isolation of the positive and negative
electrodes. Overall, the T2 of NCM batteries is lower than that of LFP
batteries, indicating that the type of cathode material significantly af­
fects T2.
The statistics of Tmax are shown in Fig. 4(c), and the findings suggest
that the values also have a significant relation to the cathode material
type and energy density. Fig. S2(w) shows the location where Tmax ap­
pears, and it does not always correspond to the center of large surface,
which suggests the necessity of multi-position layout thermocouples.
8
Applied Energy 349 (2023) 121651
According to the relevant studies, the amount of energy released during
the thermal runaway process is represented by Tmax [23,28]. It is
obvious that NCM batteries have higher Tmax than LFP batteries. Spe­
cifically, the Tmax of NCM cells ranges from 555 to 1066 ◦ C, while that of
LFP cells is in the range of 307–525 ◦ C. Moreover, among the NCM cells,
the battery with high nickel content (i.e., high energy density) tends to
exhibit a high value of Tmax, demonstrating that a great amount of en­
ergy will be released during the TR process. For example, the Tmax of
#F2 and #F3 batteries is above 1000 ◦ C, nearly twice as high as the Tmax
of 525 ◦ C for LFP batteries, while the values for #A batteries are around
600 ◦ C. Moreover, a single micro-overcharge reduces the value of Tmax,
as reported by Ref. [39]. This is due to the consumption of internal
active materials, including active lithium and electrolyte. Interestingly,
the #c2 battery has both the highest T1 value and low Tmax value,
demonstrating the excellent safety performance of this 195 Ah LFP
battery.
The location and number of temperature measurement points have
little effect on the T1 and T2 values because the temperature uniformity
at each point of the battery surface is good before the thermal runaway is
triggered. However, after the thermal runaway is activated, the het­
erogeneity of the battery temperature distribution increases signifi­
cantly, as shown in Fig. S2; currently, a multi-point arrangement of
thermocouples has been adopted to reduce the negative impact on Tmax
measurement due to the heterogeneity. Nevertheless, if the test condi­
tions allow, it is reasonable to set more thermocouples to obtain the
maximum temperature Tmax with high accuracy.
Additionally, the maximum temperature rise rate Rmax and the time
interval Δt between T1 and T2 are also significant indicators to reflect the
battery safety performance [28]. As a result, they are taken from
temperature/voltage-time curves for additional assessment, as displayed
in Fig. 4(d) and Table S4. For LFP batteries, the minimum value of Rmax
during TR is 3.2 ◦ C⋅s− 1, and the maximum value is 24.3 ◦ C⋅s− 1. However,
for NCM batteries, the minimum value of Rmax is 24.9 ◦ C⋅s− 1, and the
maximum value is 143.7 ◦ C⋅s− 1. The minimum value of Rmax for NCM
batteries is comparable to that of Rmax for LFP batteries, suggesting the
severity of the internal exothermic reactions for the former. Thus, Rmax
varies significantly with cell chemistry. Moreover, the maximum tem­
perature rise rate of the micro-overcharged cells decreases with similar
reasons for the change in Tmax.
Generally speaking, the longer the TR evolution time Δt, the better
the battery safety because of the slow self-heating process inside it. The
Δt of LFP cells are 1170.2 min, 311.2 min, 1874.9 min, 1387.8 min, and
582.3 min, respectively, as listed in Table S4. The T1 of #a2 and #c2
cells are higher than that of the other LFP batteries, it can be observed
that the Δt values are significantly lower than the other LFP batteries in
the case of comparable T2 values. As can be seen, a single temperature
indicator is biased to assess battery safety performance. For this reason,
multi-property indicators are employed to evaluate battery safety per­
formance in this study. Overall, Δt of the NCM811 + NCM523 cells,
except for the #G2 cell, is lower than NCM523 and NCM622 cells. This
demonstrates the thermal performance instability of high-nickel
batteries.
3.1.3. Quantitative assessment of safety performance
Many compulsory testing standards have been developed for batte­
ries before installation on EVs, including GB 38031–2020, SAE
J2929–2011, and UN 38.3–2011 [9,12]. The focus of standards is
whether the tested objects could pass the test. Most of the conclusions
for safety performance are either pass or fail, and no quantitative in­
dicators are given that can compare safety performance in a clear order.
According to the analysis in section 3.1.2, the characteristic parameters
during the adiabatic TR process are strongly related to the battery ma­
terial chemistry. Therefore, they are effective indicators to assess the
battery safety performance. Most importantly, the variety of parameters
can prevent the assessment from being biased. Moreover, since the two
temperature values (TM-ISC and T2) are similar, only T2 is utilized to
G. Wei et al.
avoid assessment redundancy.
In this section, we propose two indicators: TR tolerance and TR
hazards, which are determined by the Eqs. (1) and (2). Specifically, TR
tolerance involves the self-heating temperature T1, TR triggering tem­
perature T2 and TR evolution time Δt; TR hazards involve the maximum
temperature Tmax and the maximum temperature rise rate Rmax. As
analyzed in sections 3.1.1 and 3.1.2, T1 represents the beginning of
exothermic side reactions inside the battery, and T2 is the critical point
of irreversible TR issues. The transitional threshold between the three
states for the battery, i.e., normal, unstable and uncontrolled state, can
be characterized by these three sub-indicators. T1 characterizes the
temperature endurance of the battery from the normal state to the un­
stable state; T2 and Δt characterize the temperature endurance and
evolution time of the battery from the unstable state to the uncontrol­
lable state. Overall, the battery TR tolerance increases with the value of
the three mentioned sub-indicators, i.e., TR is less likely to occur. In
addition, the higher surface temperature implies a more significant
contribution of internal side reactions to heat generation. Moreover,
Tmax determines the behaviors of TR propagation in practical grouping
scenarios. The appearance of the maximum temperature rise rate Rmax is
often accompanied by a plateau or peak in the temperature rise rate
curves, as shown in Fig. 3, reflecting the intensity of the battery TR. The
resulting significant temperature rise effect is due to a synergistic effect
of exothermic side reactions and massive internal short circuit [45].
Likewise, TR hazards become more severe with the increasing values of
two sub-indicators, i.e., the impact to the adjacent batteries or electrical
units is greater after a single battery TR occurs.
( ) ( ) /
Score(TR tolerance) = T1 − T1,base + T2 − T2,base + Δt 30 (1)
( ) ( )
Score(TR hazards) = Tmax − Tmax,base + Rmax − Rmax,base
Each sub-indicator is converted into the score and summed. The
principles for scoring are as follows: T1,base is 50 ◦ C, T2,base is 120 ◦ C, and
Δt is recorded as 1 point every 30 min; Tmax,base is 300 ◦ C, Rmax,base is
3 ◦ C⋅s− 1. The calculation method fully takes into account the TR
evolutionary characteristics. Fig. 5 presents the battery intrinsic safety
performance evaluation results under adiabatic TR condition. It can be
seen that LFP batteries have a higher TR tolerance score than NCM
batteries, with values in the range of 150 to 200. As for the TR hazards
score performance, 300 is the dividing line between two types of bat­
teries. The above results demonstrate the excellent thermal stability and
low thermal threat property of LFP batteries at the cell level. For NCM
batteries, the range of the TR tolerance score is between 70 and 120.
Meanwhile, the values tend to decrease with increasing energy density.
For the #G cells that undergo a single slight overcharge test, the TR
tolerance scores decrease compared to the #F cells. As for TR hazards,
the scores of NCM batteries are distributed above 300, and the highest
Fig. 5. Safety performance evaluation results under adiabatic TR conditions. (a) TR tolerance. (b) TR hazards.
Applied Energy 349 (2023) 121651
value can reach around 900. At the same time, the TR hazards scores are
highly correlated with the nickel content of the batteries, i.e., the higher
the nickel ratio, the higher the values. The safety performance evalua­
tion results of NCM batteries at the cell level are consistent with the
comparison of thermal stability for NCM cathode materials [18].
Moreover, the #G cells exhibit lower TR hazards scores than the #F
cells, demonstrating decreased total energy stored inside the cell.
3.2. Ambient temperature, mass loss and post-disaster morphology
analysis
For both the LFP and NCM cells, the temperature difference between
the battery's various surface locations and the ARC's internal ambient
are mostly relatively consistent, as shown in Fig. S2. The critical point is
the moment that the battery TR occurs. The variability after this point is
reflected in the difference in the maximum values of the ambient tem­
perature. The ambient temperature of LFP cells rises gently without
abrupt change, except for the #c1 cell. It is related to the fact that, for
LFP cells, the ejected materials contain a large amount of high-
temperature vaporized electrolyte which is not involved in chemical
reactions [20,29]. In contrast, the ambient temperature of NCM cells
exhibits a sharp rise, demonstrating the appearance of high-temperature
gaseous decomposition substances from the internal exothermic side
reactions. As shown in Fig. 6(a), the maximum value of the ambient
temperature is strongly related to the battery cathode material and
nickel ratio. Specifically, the maximum ambient temperature of NCM
batteries is higher than that of LFP batteries; the higher the nickel ratio,
the higher the maximum value of the ambient temperature. The
maximum ambient temperature of LFP batteries during thermal
(2) runaway can be as low as about 200 ◦ C, while that of NCM811 +
NCM523 batteries reach 1000 ◦ C. The order of LFP < NCM523 <
NCM622 < NCM811 + NCM523 is followed. Moreover, the ambient
temperature of NCM cells exhibits multi-peak characteristics, as shown
in Fig. S2, which might correspond to multiple high-temperature jet fires
[49]. The above phenomena demonstrate the catastrophic feature of
nickel-rich batteries during the adiabatic TR process.
Battery TR is a thermal failure form involved with various
exothermic side reactions, resulting in the depletion of electrode mate­
rial and the ejection of gaseous production. Thus, the mass change is
closely related to the maximum temperature Tmax and the maximum
temperature rise rate Rmax, i.e., reflecting the degree of TR hazards. The
mass loss and mass loss ratio of the tested batteries are presented in
Fig. 6(b) and (c). The net mass loss of the tested LFP battery samples
increases as capacity rises. However, the LFP batteries have a mass loss
ratio of around 19%, consistent with our previous thermal runaway
suspension study on a 24 Ah LFP prismatic battery [42]. The mass loss
ratios are stable and not strongly correlated with capacity, which
9
G. Wei et al.
Fig. 6. (a) Maximum ambient temperature inside the ARC chamber during the
thermal runaway test process. (b) mass loss and mass loss ratio of LFP cells after
thermal runaway test. (c) mass loss and mass loss ratio of NCM cells after
thermal runaway test.
Fig. 7. Post-disaster residuals of the different cathode material-based cells after adiabatic thermal runaway test. (a) #a cell. (b) #A cell. (c) #D cell. (d) #F cell.
10
Applied Energy 349 (2023) 121651
illustrates that the intensity of exothermic side reactions in LFP cells
remains similar even with a significant increase in capacity. As for the
NCM batteries, the mass loss ratio exhibits a wide range. The minimum
value is about 20% (#B and #C cells), higher than the LFP cells, while
the highest value is >60% (#A, #D and #E cells). But overall, the mass
loss of NCM batteries is more significant than LFP batteries, which in­
dicates that the TR severity for NCM batteries is more extreme. More­
over, micro-overcharged cells (#G cells) have a lower mass loss ratio,
indicating lower TR hazards than normal cells (#F cells), as mentioned
in section 3.1.3.
The characteristic morphologies of each failed battery sample are
shown in Fig. 7, which can help further explore the battery TR severity.
In general, LFP batteries keep their initial appearance more preserved
than NCM batteries. Specifically, the LFP batteries keep their basic
structure after the rupture with the opening of the explosion-proof
valves to release pressure (Fig. 7(a)). However, as seen in Figs. 7(b)
and 7(c), the housing package surrounding the explosion-proof valve of
the NCM batteries even exhibits significant ablation, demonstrating the
high-temperature jet flow from the safety valve. In addition, the
aluminum package of the #F cell is severely damaged (Fig. 7(d)).
Additionally, as shown in Fig. 7(c), other surfaces of the NCM pris­
matic batteries even reveal ablation, indicating the extreme exothermic
reactions occurring here. The aluminum beads appear (Fig. 7(c)), and
the aluminum tabs fuse (Fig. 7(d)), revealing that the temperature is
higher than the melting point of aluminum (660 ◦ C) [49]. Moreover, no
intact aluminum current collector foils and separators are found, sug­
gesting significant consumption during the TR process. The identifiable
component is the red copper current collector foil (melting point:
1083.4 ◦ C) due to the exfoliation and depletion of graphite coating, as
shown in Fig. 7(d). The exfoliation of the active material is due to the
consumption of the binder involved in the side reaction.
Furthermore, the powder mixture of NCM batteries is collected, and
the microscopic morphology is observed by SEM. Meanwhile, the dis­
tribution of the surface elements is probed using EDS. As seen in Fig. S3
(see supplementary data), the distribution of the graphite and NCM
particles is disordered, suggesting the consumption of the binder
(>350 ◦ C) during the TR process [50]. In addition, the graphite elec­
trode is covered with transition metal elements (Ni, Co and Mn) of
cathode material on its surface, as shown in Figs. S4(g)-(i) (see supple­
mentary data). Even the Al element appears (Fig. S4(j)), which might be
from the cathode current collector. All the above features indicate the
significant crosstalk reaction between the electrodes [11,47], which is
one of the characteristics reflecting the violent reaction for NCM
batteries.
A comprehensive analysis, including ambient temperature, mass loss
and post-disaster morphology, shows that the TR hazards of LFP batte­
ries are lower than that of NCM batteries. Moreover, severe TR hazards
G. Wei et al.
are typically associated with high nickel content. A single micro-
overcharge leads to the lower TR hazards. The conclusions are consis­
tent with the safety performance evaluation results in section 3.1.3.
3.3. Battery venting gas analysis
3.3.1. Gas components, proportion and generation mechanism
In addition to the extremely high surface and ambient temperature
during battery TR process, a significant number of flammable and
explosive gases are also emitted. Thus, the risk evaluation of BVG is also
essential in battery safety protection engineering. Similarly, a detailed
component analysis of BVG is one of the crucial indicators for resolving
the TR chain reaction, which helps perform the necessary blocking ac­
tions at key points [51]. As a complex electrochemical system, lithium-
ion battery consists of active electrode material, separator, organic
electrolyte, metal collector and binder. In the case of high-temperature
abuse, the BVG are the product of the above components after the
crosstalk reaction. It is critical to emphasize that this study does not take
into account highly poisonous gases (e.g., HF and SO2) and electrolyte
vapors. N2, an existing inert gas in the air, does not change throughout
the adiabatic TR experiments. The corresponding component, O2, is also
removed. According to statistics, H2, CO, CO2, CH4, C2H4, C2H6, and n-
C4H10 are the major types of gas in the BVG. The result is consistent with
Refs. [29,30,52]. Specifically, all the average percentages of the above
seven types of gases are higher than 96% for both the LFP and NCM cells,
as shown in Fig. S5 (see supplementary data). Most of the results are
above 98%, which ensures that precise hazard assessment values can be
obtained and shows good consistency in the results of multiple gas
collection tests. During the battery TR evolution process, the BVG
mentioned above comes from the following main reactions:
3.3.1.1. Reaction of SEI decomposition – H2, CO, CO2 and hydrocarbon
gases. When exposed to high temperature, LEDC ((CH2OCO2Li)2), which
is the primary organic component during the early stage of SEI film
formation, decomposes into Li2CO3, CO2, and C2H4 [17,53]. The
decomposition of PEO oligomer ((–CH2–CH2–O–)n) is mainly through
random chain scission of the backbone to generate CO, H2, CH4 and
C2H4 [17,54]. Moreover, the decomposition of ROCO2Li produces CO2
and the stable inorganic lithium salt Li2CO3 [54].
LEDC→Li2 CO3 + CO2 + C2 H4 + 0.5O2 (3)
LEDC + 2Li→2Li2 CO3 + C2 H4 (4)
PEO→H2 + CHx + CO + H2 O + ( − CH2 − O − )n− (5)
2
2ROCO2 Li + H2 O→Li2 CO3 + CO2 + 2LiOR (6)
3.3.1.2. Reaction between the lithiated graphite and electrolyte - hydro­
carbon gases. When the passivation layer surrounding the graphite-
based negative electrode is destroyed, the electrode reacts when it
comes into contact with the electrolyte, regenerating the SEI film [42].
The chemical reactions of the primary solvents with lithiated graphite
are as follows [17,42]. The gases released by the reaction are C2H4 and
C2H6, etc.
2LiC6 + 2C3 H4 O3 (EC)→LEDC + C2 H4 + 2C6 (7)
2LiC6 + C5 H10 O3 (DEC)→Li2 CO3 + C2 H4 + C2 H6 + 2C6 (8)
3.3.1.3. Reaction of electrolyte decomposition – HF and CO2. Lithium
salts are subject to pyrolysis [17] and hydrolysis in the presence of traces
of water [10]. The reactions mentioned above are as follows [10,42].
The generated strong Lewis acid, i.e., PF5, tends to corrode the organic
SEI membrane components, thus accelerating the generation of hydro­
carbon gases [55].
11
Applied Energy 349 (2023) 121651
LiPF6 →LiF + PF5 (9)
LiPF6 + H2 O→LiF + POF 3 + 2HF (10)
PF5 + H2 O→POF 3 + 2HF (11)
In addition, with the participation of oxygen from the phase change
of cathode material [18], organic solvents are oxidized, releasing CO2 by
the following reactions [52].
C3 H4 O3 (EC) + 2.5O2 →3CO2 + 2H2 O (12)
C5 H10 O3 (DEC) + 6O2 →5CO2 + 5H2 O (13)
3.3.1.4. Reaction between the active lithium and binder - H2. As the in­
ternal temperature continues to rise, a large amount of highly reactive
lithium leaches out of the lithiated graphite, which then reacts
exothermically with the binder and releases H2 [54]. A similar chemical
reaction involved another commonly used binder CMC is as follows
[52].
Li + − CH2 − CF2 − →0.5H2 + LiF + − CH = CF − (14)
Li + CMC − OH→CMC − OLi + 0.5H2 (15)
3.3.1.5. Reaction of electrode material decomposition - O2. For NCM cells,
the important source of O2 is the irreversible phase change of cathode
material. NCM cathode first undergoes a transition from a layered
structure (space group R3m) to a spinel structure (space group Fd3m)
and finally to a rock salt phase (space group Fm3m), even including the
metallic phase [10]. Although LFP is a generally safe cathode material,
several studies have shown that it can decompose and release oxygen
[10,50], as shown in Eq. (17). In the 400–1200 ◦ C range, according to
Ref. [56], graphite interacts with oxygen to release carbon dioxide,
which might be another cause of the significant amount of CO2 for NCM
batteries.
NCM(R3m)→(Mn, Ni)O(Fm3m) + CoO + Ni + O2 (16)
2Li0 FePO4 →Fe2 P2 O7 + 0.5O2 (17)
Fig. 8 shows the volume proportion of each gas among the BVG. The
amount of H2 for LFP batteries varies from 27% to 52%, much larger
than that for NCM batteries (12%–20%). Among the NCM batteries, the
volume proportion of H2 for higher-nickel-based batteries is slightly
lower. The result is consistent with Ref. [32]. Hydrocarbon gases exhibit
similar characteristics to hydrogen. Additionally, for LFP batteries, the
percentage of H2 is around equal to the sum percentage of CO2 and CO,
where the volume of CO (4%–9%) is not significant. On the contrary, the
total proportion of CO2 and CO for NCM batteries is greater than that of
H2, ranging from 66%–79%, demonstrating that the oxidation of NCM
batteries' BVG is higher than that of LFP batteries. Moreover, NCM
batteries with higher nickel content have a higher sum volume of CO2
and CO. Micro-overcharge impacts little on the volume proportion of
each gas. It can be seen that the concentration of CO (25%–32%) for
NCM batteries is significantly more than that for LFP batteries.
Considering that the LELs of CO (12.5%) is much higher than that of H2
(4%) [30], it can be speculated that the BVG explosion risk of NCM
batteries will be lower than that of LFP batteries. Although CO2 is not
combustible, it affects the flammability of other gases; in addition, high
concentrations of CO2 in local spaces harm vehicle occupants' health. It
should be noted that there is some uncertainty in the determination of
gas ratios. Still, the adverse effects of this uncertainty have been mini­
mized by specific measures in this paper. Triggering thermal runaways
in a limited space and rapid, multiple gas collection retains the original
composition of BVG to a great extent. However, if test conditions permit,
an attempt can be made to further reduce the effect of the air on BVG
G. Wei et al.
Fig. 8. BVG components and proportions obtained by GC tests. (a) LFP cells. (b) NCM cells.
components by pre-displacing the air inside the test chamber with inert
gases.
Furthermore, the seven types of gas are divided into two groups, one
of which is H2 and hydrocarbon gases (e.g., CH4–5% and C2H4–2.7%)
with low LELs and the other is carbon oxides. Fig. 9 shows the re­
lationships between the proportions of the above two gas groups and
battery energy density. The fitting line shows that the total proportion of
H2 and hydrocarbon gases is negatively related to the energy density
Fig. 9. Relationship between the gas proportion and battery energy density. (a)
the total proportion of hydrogen and hydrocarbon gases versus energy density.
(b) the total proportion of carbon monoxide and carbon dioxide versus en­
ergy density.
12
Applied Energy 349 (2023) 121651
with a slope coefficient of − 0.21. While for the total proportion of CO2
and CO, it demonstrates a positive correlation with battery energy
density, and the slope of the fitting line is 0.21. The described correla­
tion is particularly apparent in the high energy density range. In other
words, the above conclusions are particularly applicable to NCM bat­
teries. As mentioned in Refs. [18,19], LFP olivine material has a stable
P–O covalent bond, ensuring less oxygen release; on the contrary, the
NCM layered material has a polar transition metal‑oxygen bond causing
significant oxygen release, and the situation worsens with increasing
nickel content. During the TR process, the generation of CO has high
priority and thus captures the most C atoms, reducing the generation
probability of the hydrocarbon gases [32]. Therefore, as energy density
increases, i.e., a more significant amount of oxygen appears, part of the
electrolyte is involved in the oxidation reaction, and the total pro­
portions of CO2 and CO grow. Since the amount of electrolyte is limited,
the intensity of its reaction with the intercalated lithium is relatively
weakened, leading to decreased hydrocarbon gases content. In addition,
according to the latest mechanism study by Ouyang's team [51], during
the initial heat accumulation stage of thermal runaway, the reductive
gases generated at the anode-electrode interface will lead to significant
changes in the surface morphology and lattice structure of high nickel-
cathode material even at 100 ◦ C, resulting in a substantial increase in
the content of carbon dioxide. Therefore, for high-nickel batteries, the
above mechanisms, i.e., generating oxidative gases in both the low-
temperature and high-temperature ranges, can explain that the
amount of oxidative gases positively correlates with the battery energy
density.
3.3.2. Theoretical calculation on the lower explosion limits of battery
venting gas
Obviously, the above speculation (i.e., the BVG explosion risk of
NCM batteries is lower than that of LFP batteries) is contrary to the
established knowledge and previous safety performance evaluation re­
sults of this research, i.e., the TR hazards of LFP batteries is lower than
that of NCM batteries. To further determine the correctness of this
speculation, theoretical calculation of explosion hazards of BVG is car­
ried out in this section. LELs, i.e., the lowest concentration of BVG that
can be ignited in the air, is an important indicator to evaluate the
explosibility and flammability of combustible gases, as well as the
guidance for battery safety design. The calculation method employed is
G. Wei et al.
an empirical formula (Eq. (19)) based on Le-Chatelier's law (Eq. (18))
[57]. The results calculated by this method have been shown to be in
good agreement with the results of practical LEL test experiments
[34,38].
1
LELmix = ∑
n (18)
xi
LELi
i=1
where xi is the volume proportion of particular component i in the BVG;
LELi is the LEL value of the particular component i in the BVG; n is the
number of gas types; LELmix is the LEL value of BVG.
( )
1 + 1−BB • 100
LEL′mix = LELmix • (19)
100 + LELmix • 1−BB
where B is the inert gas volume proportion in the BVG and LEL′mix is the
LEL value of BVG considering the inert gas.
Fig. 10 shows the calculated result of LEL. The LEL of BVG for LFP
batteries is around 6%–7.5%, while that for NCM batteries is in the range
of 8% to 11.5%. The result demonstrates that the explosion hazards of
BVG for LFP batteries are higher than that for NCM batteries, which is
consistent with the findings in Ref. [33]. Obviously, the significant
amount of hydrogen and hydrocarbon gases with low LELs are to blame
for the high deflagration risks of BVG from failure LFP batteries.
Moreover, it is found that NCM batteries with higher nickel content have
a higher LEL value of BVG, which means that the increased energy
density reduces the deflagration risk from the perspective of gas
explosibility. In addition, a single micro-overcharge has little effect on
the LEL value of BVG. As more and more LFP batteries are used in the
field of energy storage systems and electric transportation applications,
the above issue should be paid enough attention to regarding battery
safety prevention and control work. For example, at the module and
pack level, the timely gas release through the proper design of the vent
valve [11] and the purging from the specific flow rate of airflow are
provided to dilute the BVG concentration. Besides, regarding the spatial
location of the pole and safety valve at the cell level, existing prismatic
batteries generally follow the pattern of being located on the same side,
greatly increasing the probability of contact between the BVG and high-
temperature electrical elements. Therefore, in the next generation of
battery safety protection design, the concept of “thermoelectric sepa­
ration” can be applied, i.e., the opposite or adjacent side of the pole and
safety valve distribution. Combined with the directional pressure relief
channel, it is expected to significantly avoid the secondary explosion
hazards caused by the venting mixture of the failed battery.
4. Conclusions and future research orientations
This paper examines the commercial-size lithium-ion battery
Fig. 10. Theoretical LEL values of the BVG.
13
Applied Energy 349 (2023) 121651
thermal runaway issues from two perspectives, specifically including the
battery intrinsic safety performance and venting gas explosion hazards.
Initially, batteries with LiFePO4 and LiNixCoyMnzO2 (x from 0.5 to 0.8)
cathode materials, as well as the micro-overcharged cells, are used to
perform adiabatic TR tests. Multi-property sub-indicators are extracted
to describe the battery thermal stability. Based on this, a battery safety
performance (TR tolerance and TR hazards) calculation method, which
fully takes into account the TR evolution characteristics, is introduced.
Then, a profound insight into the battery failure severity is acquired
through the analysis including morphology, mass loss and ambient
temperature. Moreover, the main BVG components are studied through
the gas chromatograph analysis, and the BVG explosion characteristics
are calculated theoretically. The main conclusions are as follows:
(1) The TR tolerance score of LFP batteries is higher than that of NCM
batteries, suggesting former's excellent intrinsic thermal stability
at the cell level. As for the TR hazards score, it shows a strong
correlation with energy density, following the order of LFP <
NCM523 < NCM622 < NCM811 + NCM523, which is proved by
poorer structural integrity, greater mass loss ratio and higher
ambient temperature for rich-nickel batteries.
(2) The BVG primarily consists of H2, CO, CO2 and hydrocarbon
gases. For LFP batteries, the amount of H2 is found to be larger
than CO. On the contrary, for NCM batteries, the total proportion
of CO and CO2 is significant, and the volume fraction of CO is
more than that of H2. Among NCM batteries, the higher the nickel
content, the greater the total proportion of CO and CO2 and the
lower the amount of H2. Hydrocarbon gases exhibit a similar
trend to H2.
(3) The theoretical LEL value of BVG for LFP batteries is lower than
that of NCM batteries, which suggests the BVG from LFP batteries
is more likely to trigger the explosion hazards. Moreover, as the
nickel ratio increases, the deflagration risk of BVG from NCM
batteries becomes lower.
(4) A single micro-overcharge process leads to NCM cells with lower
TR tolerance and TR hazards but has little effect on BVG com­
ponents and LEL values.
The following issues remain to be carried out in future research:
(1) To retain the original BVG components as much as possible, the
intrinsic gases already present in the ARC chamber should be
replaced with alternative inert gases, such as argon.
(2) The BVG explosibility of failed batteries under various states (e.
g., state of charge and state of health) needs to be evaluated
comprehensively.
(3) At present, the experimental objects are single cells. Thus, it is
necessary to carry out thermal runaway propagation experiments
with battery modules or packs.
(4) The thermal runaway-induced method in this paper is over­
heating. To explore the effect of triggering type on the BVG
explosibility, the electrical and mechanical abuse experiments
need to be performed.
CRediT authorship contribution statement
Gang Wei: Writing – review & editing, Writing – original draft,
Validation, Methodology, Formal analysis, Data curation, Conceptuali­
zation. Ranjun Huang: Writing – review & editing, Methodology.
Guangxu Zhang: Writing – review & editing, Methodology. Bo Jiang:
Writing – review & editing. Jiangong Zhu: Writing – review & editing.
Yangyang Guo: Methodology. Guangshuai Han: Validation, Supervi­
sion, Resources, Methodology, Conceptualization. Xuezhe Wei: Super­
vision, Project administration, Funding acquisition. Haifeng Dai:
Writing – review & editing, Supervision, Resources, Project adminis­
tration, Methodology, Investigation, Funding acquisition,
G. Wei et al.
Conceptualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgement
This work was supported by the Program of Shanghai Academic/
Technology Research Leader (grant number 22XD1423800) and the
National Natural Science Foundation of China (grant numbers
52176199, U20A20310).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.apenergy.2023.121651.
References
[1] Ding T, Sun Y, Huang C, et al. Pathways of clean energy heating electrification
programs for reducing carbon emissions in Northwest China. Renew Sustain
Energy Rev 2022;166:112679.
[2] Dai H, Jiang B, Hu X, et al. Advanced battery management strategies for a
sustainable energy future: multilayer design concepts and research trends. Renew
Sustain Energy Rev 2020;138:110480.
[3] Qiao D, Wang X, Lai X, et al. Online quantitative diagnosis of internal short circuit
for lithium-ion batteries using incremental capacity method. Energy 2022;243:
123082.
[4] Zhu J, Wang Y, Huang Y, et al. Data-driven capacity estimation of commercial
lithium-ion batteries from voltage relaxation. Nat Commun 2022;13:2261.
[5] Jiang B, Zhu Y, Zhu J, et al. An adaptive capacity estimation approach for lithium-
ion battery using 10-min relaxation voltage within high state of charge range.
Energy 2023;263:125802.
[6] Wang Y, Ren D, Feng X, et al. Thermal runaway modeling of large format high-
nickel/silicon-graphite lithium-ion batteries based on reaction sequence and
kinetics. Appl Energy 2022;306:117943.
[7] Li D, Liu P, Zhang Z, et al. Battery thermal runaway fault prognosis in electric
vehicles based on abnormal heat generation and deep learning algorithms. IEEE
Trans Power Electron 2022;37:8513–25.
[8] Ren D, Hsu H, Li R, et al. A comparative investigation of aging effects on thermal
runaway behavior of lithium-ion batteries. eTransportation 2019;2:100034.
[9] Feng X, Ouyang M, Liu X, et al. Thermal runaway mechanism of lithium ion battery
for electric vehicles: a review. Energy Stor Mater 2018;10:246–67.
[10] Wang Q, Mao B, Stoliarov SI, et al. A review of lithium ion battery failure
mechanisms and fire prevention strategies. Prog Energy Combust Sci 2019;73:
95–131.
[11] Feng X, Ren D, He X, et al. Mitigating thermal runaway of Lithium-ion batteries.
Joule 2020;4:743–70.
[12] Duan J, Tang X, Dai H, et al. Building safe lithium-ion batteries for electric
vehicles: a review. Electrochem Energy Rev 2020;3:1–42.
[13] Zhu X, Wang H, Wang X, et al. Internal short circuit and failure mechanisms of
lithium-ion pouch cells under mechanical indentation abuse conditions:An
experimental study. J Power Sources 2020;455:227939.
[14] Zhang G, Wei X, Chen S, et al. Unlocking the thermal safety evolution of lithium-
ion batteries under shallow over-discharge. J Power Sources 2022;521:230990.
[15] Zhang G, Wei X, Zhu J, et al. Revealing the failure mechanisms of lithium-ion
batteries during dynamic overcharge. J Power Sources 2022;543:231867.
[16] Gerardine REW, Bottea G, Zhang Zhengming. Thermal stability of LiPF6–EC⋅EMC
electrolyte for lithium ion batteries. J Power Sources 2001;97–98:570–5.
[17] Zheng Y, Shi Z, Ren D, et al. In-depth investigation of the exothermic reactions
between lithiated graphite and electrolyte in lithium-ion battery. J Energy Chem
2022;69:593–600.
[18] Bak SM, Hu E, Zhou Y, et al. Structural changes and thermal stability of charged
LiNixMnyCozO2 cathode materials studied by combined in situ time-resolved XRD
and mass spectroscopy. ACS Appl Mater Interfaces 2014;6:22594–601.
[19] El Moutchou S, Aziam H, Mansori M, et al. Thermal stability of lithium-ion
batteries: case study of NMC811 and LFP cathode materials. Mater Today: Proc
2022;51:A1–7.
[20] Zhou Z, Ju X, Zhou X, et al. A comprehensive study on the impact of heating
position on thermal runaway of prismatic lithium-ion batteries. J Power Sources
2022;520:230919.
14
Applied Energy 349 (2023) 121651
[21] Jhu CY, Wang YW, Shu CM, et al. Thermal explosion hazards on 18650 lithium ion
batteries with a VSP2 adiabatic calorimeter. J Hazard Mater 2011;192:99–107.
[22] Zhong G, Mao B, Wang C, et al. Thermal runaway and fire behavior investigation of
lithium ion batteries using modified cone calorimeter. J Therm Anal Calorim 2018;
135:2879–89.
[23] Feng X, Fang M, He X, et al. Thermal runaway features of large format prismatic
lithium ion battery using extended volume accelerating rate calorimetry. J Power
Sources 2014;255:294–301.
[24] Zhang Y, Wang H, Li W, et al. Size distribution and elemental composition of vent
particles from abused prismatic Ni-rich automotive lithium-ion batteries. J Energy
Stor 2019;26:100991.
[25] Kriston A, Kersys A, Antonelli A, et al. Initiation of thermal runaway in Lithium-ion
cells by inductive heating. J Power Sources 2020;454:227914.
[26] Shironita S, Tsuruga H, Honda K, et al. Thermal runaway characteristics of a
LiFePO4-based lithium-ion secondary battery using the laser-irradiation method.
J Energy Stor 2021;40:102715.
[27] Walker WQ, Cooper K, Hughes P, et al. The effect of cell geometry and trigger
method on the risks associated with thermal runaway of lithium-ion batteries.
J Power Sources 2022;524:230645.
[28] Feng X, Zheng S, Ren D, et al. Investigating the thermal runaway mechanisms of
lithium-ion batteries based on thermal analysis database. Appl Energy 2019;246:
53–64.
[29] Jia Z, Song L, Mei W, et al. The preload force effect on the thermal runaway and
venting behaviors of large-format prismatic LiFePO4 batteries. Appl Energy 2022;
327:120100.
[30] Qin P, Jia Z, Wu J, et al. The thermal runaway analysis on LiFePO4 electrical
energy storage packs with different venting areas and void volumes. Appl Energy
2022;313:118767.
[31] Zhang Y, Cheng S, Mei W, et al. Understanding of thermal runaway mechanism of
LiFePO4 battery in-depth by three-level analysis. Appl Energy 2023;336:120695.
[32] Yang X, Wang H, Li M, et al. Experimental study on thermal runaway behavior of
Lithium-ion battery and analysis of combustible limit of gas production. Batteries
2022;8:250.
[33] Wang H, Xu H, Zhang Z, et al. Fire and explosion characteristics of vent gas from
lithium-ion batteries after thermal runaway: A comparative study. eTransportation
2022;13:100190.
[34] Baird AR, Archibald EJ, Marr KC, et al. Explosion hazards from lithium-ion battery
vent gas. J Power Sources 2020;446:227257.
[35] Wang G, Kong D, Ping P, et al. Revealing particle venting of lithium-ion batteries
during thermal runaway: A multi-scale model toward multiphase process.
eTransportation 2023;16:100237.
[36] Peng Y, Yang L, Ju X, et al. A comprehensive investigation on the thermal and toxic
hazards of large format lithium-ion batteries with LiFePO(4) cathode. J Hazard
Mater 2020;381:120916.
[37] Yuan L, Dubaniewicz T, Zlochower I, et al. Experimental study on thermal runaway
and vented gases of lithium-ion cells. Proc Safe Environ Protect 2020;144:186–92.
[38] Chen S, Wang Z, Wang J, et al. Lower explosion limit of the vented gases from Li-
ion batteries thermal runaway in high temperature condition. J Loss Prev Process
Ind 2020;63:103992.
[39] Zhang G, Wei X, Chen S, et al. Comprehensive investigation of a slight overcharge
on degradation and thermal runaway behavior of Lithium-ion batteries. ACS Appl
Mater Interfaces 2021;13:35054–68.
[40] Wang H, Du Z, Rui X, et al. A comparative analysis on thermal runaway behavior of
Li (NixCoyMnz) O2 battery with different nickel contents at cell and module level.
J Hazard Mater 2020;393:122361.
[41] Fu Y, Lu S, Shi L, et al. Combustion characteristics of electrolyte Pool fires for
Lithium ion batteries. J Electrochem Soc 2016;163:A2022–8.
[42] Tang X, Zhang G, Wang X, et al. Investigating the critical characteristics of thermal
runaway process for LiFePO4/graphite batteries by a ceased segmented method.
iScience 2021;24:103088.
[43] Finegan DP, Scheel M, Robinson JB, et al. In-operando high-speed tomography of
lithium-ion batteries during thermal runaway. Nat Commun 2015;6:6924.
[44] Mao B, Chen H, Cui Z, et al. Failure mechanism of the lithium ion battery during
nail penetration. Int J Heat Mass Transf 2018;122:1103–15.
[45] Ren D, Feng X, Liu L, et al. Investigating the relationship between internal short
circuit and thermal runaway of lithium-ion batteries under thermal abuse
condition. Energy Stor Mater 2021;34:563–73.
[46] Liu L, Feng X, Rahe C, et al. Internal short circuit evaluation and corresponding
failure mode analysis for lithium-ion batteries. J Energy Chem 2021;61:269–80.
[47] Liu X, Ren D, Hsu H, et al. Thermal runaway of Lithium-ion batteries without
internal short circuit. Joule 2018;2:2047–64.
[48] Lee H, Yanilmaz M, Toprakci O, et al. A review of recent developments in
membrane separators for rechargeable lithium-ion batteries. Energ Environ Sci
2014;7:3857–86.
[49] Shan T, Wang Z, Zhu X, et al. Explosion behavior investigation and safety
assessment of large-format lithium-ion pouch cells. J Energy Chem 2022;72:
241–57.
[50] Jia Z, Qin P, Li Z, et al. Analysis of gas release during the process of thermal
runaway of lithium-ion batteries with three different cathode materials. J Energy
Stor 2022;50:104302.
[51] Wang Y, Feng X, Peng Y, et al. Reductive gas manipulation at early self-heating
stage enables controllable battery thermal failure. Joule 2022;6:2810–20.
[52] Golubkov AW, Fuchs D, Wagner J, et al. Thermal-runaway experiments on
consumer Li-ion batteries with metal-oxide and olivin-type cathodes. RSC Adv
2014;4:3633–42.
G. Wei et al.
[53] Kriston A, Adanouj I, Ruiz V, et al. Quantification and simulation of thermal
decomposition reactions of Li-ion battery materials by simultaneous thermal
analysis coupled with gas analysis. J Power Sources 2019;435:226774.
[54] Liu X, Yin L, Ren D, et al. In situ observation of thermal-driven degradation and
safety concerns of lithiated graphite anode. Nat Commun 2021;12:4235.
15
View publication stats
Applied Energy 349 (2023) 121651
[55] Yang H, Bang H, Amine K, et al. Investigations of the exothermic reactions of
natural graphite anode for Li-ion batteries during thermal runaway. J Electrochem
Soc 2005;152:A73–9.
[56] Xiaowei L, Jean-Charles R, Suyuan Y. Effect of temperature on graphite oxidation
behavior. Nucl Eng Des 2004;227:273–80.
[57] Mashuga CV, Crowl DA. Derivation of Le Chatelier’s mixing rule for flammable
limits. Proc Safety Prog 2000;19:112–7.